Crystal structure of
2-(4-chloro-benzamido)benzoic acid
Rodolfo Moreno-Fuquen,a* Vanessa Meloaand Javier Ellenab
aDepartamento de Quı´mica - Facultad de Ciencias Naturales y Exactas, Universidad
del Valle, Apartado 25360, Santiago de Cali, Colombia, andbInstituto de Fı´sica de
Sa˜o Carlos, IFSC, Universidade de Sa˜o Paulo, USP, Sa˜o Carlos, SP, Brazil. *Correspondence e-mail: rodimo26@yahoo.es
Received 22 September 2015; accepted 23 September 2015
Edited by E. R. T. Tiekink, University of Malaya, Malaysia
In the title molecule, C14H10ClNO3, the amide C O bond is antito theo-carboxy substituent in the adjacent benzene ring, a conformation that facilitates the formation of an intra-molecular amide-N—H O(carbonyl) hydrogen bond that closes anS(6) loop. The central amide segment is twisted away from the carboxy- and chloro-substituted benzene rings by 13.93 (17) and 15.26 (15), respectively. The most prominent supramolecular interactions in the crystal packing are carb-oxylic acid-H O(carboxyl) hydrogen bonds that lead to centrosymmetric dimeric aggregates connected by eight-membered { HOC O}2synthons.
Keywords:crystal structure; carboxylic acid; amide; hydrogen bonding.
CCDC reference:1427117
1. Related literature
For our studies on the effects of substituents on the structures of N-(aryl)-amides, see: Moreno-Fuquenet al. (2014, 2015). For benzanilide properties, see: Nuta et al. (2013); Leander (1992); Ahleset al.(2004). For related structures, see: Saeedet al. (2008, 2010); Rodrigues et al. (2011). For hydrogen bonding, see: Desiraju & Steiner (1999), Nardelli (1995).
2. Experimental
2.1. Crystal data
C14H10ClNO3
Mr= 275.69 MonoclinicC2=c a= 26.8843 (10) A˚
b= 5.0367 (2) A˚
c= 20.9264 (12) A˚
= 117.489 (2)
V= 2513.7 (2) A˚3
Z= 8
MoKradiation
= 0.31 mm1
T= 295 K
0.400.080.06 mm
2.2. Data collection
Nonius KappaCCD diffractometer 4248 measured reflections 2295 independent reflections
1049 reflections withI> 2(I)
Rint= 0.057
2.3. Refinement
R[F2> 2(F2)] = 0.043
wR(F2) = 0.132
S= 0.92 2295 reflections 176 parameters
H atoms treated by a mixture of independent and constrained refinement
max= 0.20 e A˚
3 min=0.19 e A˚
3
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
N1—NH1 O2 0.93 (3) 1.96 (3) 2.678 (3) 133 (3) O3—OH3 O2i
0.82 1.83 2.645 (3) 175
Symmetry code: (i)xþ3 2;yþ
3 2;zþ1.
Data collection:COLLECT (Nonius, 2000); cell refinement:HKL SCALEPACK(Otwinowski & Minor, 1997); data reduction:HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics:ORTEP-3 for Windows(Farrugia, 2012) andMercury(Macraeet al., 2006); software used to prepare material for publication:SHELXL2014/7.
Acknowledgements
RMF is grateful to the Universidad del Valle, Colombia, for partial financial support.
Supporting information for this paper is available from the IUCr electronic archives (Reference: TK5391).
data reports
References
Ahles, T. A., Herndon, J. E., Small, E. J., Vogelzang, N. J., Kornblith, A. B., Ratain, M. J., Stadler, W. S., Palchak, D., Marshall, E., Wilding, G., Petrylak, D. & Holland, C. (2004).Cancer,101, 2202–2208.
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond. Oxford University Press, pp. 86-89.
Farrugia, L. J. (2012).J. Appl. Cryst.45, 849–854. Leander, J. D. (1992).Epilepsia,33, 705-711.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006).J. Appl. Cryst.39, 453–457. Moreno-Fuquen, R., Azca´rate, A. & Kennedy, A. R. (2014).Acta Cryst.E70,
o344.
Moreno-Fuquen, R., Azca´rate, A. & Kennedy, A. R. (2015).Acta Cryst.E71, o389–o390.
Nardelli, M. (1995).J. Appl. Cryst.28, 659.
Nonius (2000).COLLECT. Nonius BV, Delft, The Netherlands.
Nuta, D. C., Chifiriuc, A. C., Draghici, C., Limban, C., Missir, A. V. & Morusciag, L. (2013).Farmacia (Bucarest),61, 966–974.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Rodrigues, V. Z., Kuckova´, L., Gowda, B. T. & Kozˇı´sˇek, J. (2011).Acta Cryst.
E67, o3171.
Saeed, A., Khera, R. A., Abbas, N., Gotoh, K. & Ishida, H. (2008).Acta Cryst.
E64, o2043.
Saeed, A., Khera, R. A. & Simpson, J. (2010).Acta Cryst.E66, o214. Sheldrick, G. M. (2008).Acta Cryst.A64, 112–122.
supporting information
sup-1 Acta Cryst. (2015). E71, o856–o857
supporting information
Acta Cryst. (2015). E71, o856–o857 [https://doi.org/10.1107/S2056989015017879]
Crystal structure of 2-(4-chlorobenzamido)benzoic acid
Rodolfo Moreno-Fuquen, Vanessa Melo and Javier Ellena
S1. Comment
The crystal structure determination of 2-(4-chlorobenzamido)benzoic acid, (I), was investigated in a continuation of our
studies on substituted N-phenyl benzamides which have been synthesized from picryl esters. This study was also
performed to study the effect of substituents on the structures of benzanilides (Moreno-Fuquen et al., 2014, 2015).
Benzanilide systems are used as antimicrobial drugs (Nuta et al., 2013), as anticonvulsants (Leander, 1992) or as
treatment for patients with prostate carcinoma (Ahles et al., 2004). Structures of similar molecules were compared with
(I), i.e. 4-chloro-N-(2-methoxyphenyl)benzamide (Saeed et al., 2010), 4-chloro-N-phenylbenzamide (Rodrigues et al.,
2011) and 4-chloro-N-(o-tolyl)benzamide (Saeed et al., 2008). The molecular structure of (I) is shown in Fig. 1. The C═O
bond is anti to the o-carboxy substituent in the benzoyl ring. The N—H and C=O bonds in the central amide group are
also anti to each other. Comparing (I) with the three aforementioned structures reveals that significant differences in bond
lengths and bond angles are not observed. The central amide segment (C1-C7(O1)-N1-C8) is twisted away from the
carb-oxy- and chloro-substituted benzene rings by 13.93 (17) and 15.26 (15)°, respectively. Molecules of (I) are held together
by intermolecular O—H···O hydrogen bonds of moderate strength (Desiraju & Steiner, 1999). The O3 atom is linked to
O2i atom (i = -x+3/2, -y+3/2, -z+1) with O···O distances of 2.645 (2), (see Table 1, Nardelli, 1995). Except for the
presence of hydrogen bonding in the formation of dimer, no other significant intermolecular interactions are observed in
the structure.
S2. Experimental
2,4,6-Trinitrophenyl 4-chlorobenzoate (0.060 g, 0.163 mmol) and 2-carboxyaniline (0.045 g, 0.328 mmol) were dissolved
in toluene (15 ml) and stirred for 6 h under reflux. On completion of the reaction part of the solvent was evaporated and a
crystalline yellow solid was obtained; m.p. 470 (1) K.
S3. Refinement
All H-atoms were located in difference Fourier maps and were positioned geometrically [C—H = 0.93 Å] and were
refined using a riding-model approximation with Uiso(H) constrained to 1.2Ueq(C). The O-bound H atoms was similarly
fixed with O—H = 0.82 Å, and with Uiso(H) constrained to 1.5Ueq(O). The N-bound H atom was found from the Fourier
Figure 1
The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as
spheres of arbitrary radius.
2-(4-Chlorobenzamido)benzoic acid
Crystal data
C14H10ClNO3 Mr = 275.69
Monoclinic, C2/c a = 26.8843 (10) Å
b = 5.0367 (2) Å
c = 20.9264 (12) Å
β = 117.489 (2)°
V = 2513.7 (2) Å3
Z = 8
F(000) = 1136
Dx = 1.457 Mg m−3 Melting point: 470(1) K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2553 reflections
θ = 3.1–25.4°
µ = 0.31 mm−1 T = 295 K Needle, yellow 0.40 × 0.08 × 0.06 mm
Data collection
Nonius KappaCCD diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
CCD rotation images, thick slices scans 4248 measured reflections
2295 independent reflections
1049 reflections with I > 2σ(I)
Rint = 0.057
θmax = 25.4°, θmin = 3.1°
h = −31→32
k = −6→6
l = −25→24
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.043 wR(F2) = 0.132 S = 0.92
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
supporting information
sup-3 Acta Cryst. (2015). E71, o856–o857
w = 1/[σ2(F
o2) + (0.0632P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
Δρmax = 0.20 e Å−3 Δρmin = −0.19 e Å−3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.74640 (9) −0.2731 (4) 0.30942 (12) 0.0824 (7)
C5 0.90834 (14) −0.0840 (7) 0.34839 (18) 0.0786 (9)
H5 0.9265 −0.1847 0.3282 0.094*
C10 0.58970 (13) −0.0955 (6) 0.29315 (17) 0.0739 (9)
H10 0.5647 −0.2205 0.2623 0.089*
C9 0.64347 (12) −0.0846 (5) 0.30083 (15) 0.0623 (8)
H9 0.6543 −0.2008 0.2750 0.075*
C2 0.85453 (13) 0.2133 (6) 0.40771 (18) 0.0766 (9)
H2 0.8366 0.3155 0.4280 0.092*
C11 0.57224 (13) 0.0750 (6) 0.33029 (18) 0.0754 (9)
H11 0.5357 0.0667 0.3242 0.090*
C6 0.85319 (14) −0.1349 (6) 0.33124 (17) 0.0730 (9)
H6 0.8344 −0.2716 0.2993 0.088*
C3 0.90974 (14) 0.2649 (6) 0.42543 (18) 0.0801 (10)
H3 0.9289 0.4004 0.4577 0.096*
C4 0.93606 (13) 0.1173 (7) 0.39566 (17) 0.0701 (9)
NH1 0.7536 (13) 0.280 (6) 0.3758 (17) 0.102 (11)*
Cl1 1.00534 (4) 0.1835 (2) 0.41722 (6) 0.1062 (4)
N1 0.73632 (10) 0.1205 (5) 0.35559 (12) 0.0592 (7)
O3 0.67865 (8) 0.6206 (3) 0.46790 (10) 0.0688 (6)
OH3 0.7015 0.7286 0.4949 0.103*
O2 0.75129 (8) 0.5079 (3) 0.45041 (10) 0.0641 (6)
C14 0.70192 (12) 0.4755 (5) 0.43671 (14) 0.0548 (7)
C8 0.68169 (11) 0.1015 (5) 0.34751 (14) 0.0529 (7)
C7 0.76554 (12) −0.0609 (6) 0.33845 (15) 0.0599 (7)
C13 0.66432 (11) 0.2748 (5) 0.38605 (14) 0.0535 (7)
C1 0.82537 (12) 0.0120 (5) 0.36030 (15) 0.0568 (7)
C12 0.60946 (12) 0.2573 (6) 0.37640 (15) 0.0664 (8)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.0839 (16) 0.0631 (13) 0.1073 (17) −0.0111 (11) 0.0502 (14) −0.0225 (12)
C5 0.075 (2) 0.090 (2) 0.083 (2) 0.0100 (19) 0.047 (2) −0.004 (2)
C10 0.063 (2) 0.071 (2) 0.072 (2) −0.0093 (16) 0.0174 (18) 0.0023 (17)
C9 0.063 (2) 0.0595 (17) 0.0591 (19) −0.0054 (15) 0.0242 (16) −0.0031 (15)
C2 0.066 (2) 0.081 (2) 0.090 (2) −0.0010 (17) 0.0417 (18) −0.0156 (19)
C11 0.056 (2) 0.083 (2) 0.083 (2) −0.0118 (18) 0.0279 (18) −0.0009 (19)
C6 0.080 (2) 0.072 (2) 0.074 (2) 0.0010 (17) 0.0420 (19) −0.0089 (16)
C3 0.066 (2) 0.085 (2) 0.089 (2) −0.0102 (17) 0.035 (2) −0.0121 (19)
C4 0.0581 (19) 0.083 (2) 0.073 (2) 0.0059 (17) 0.0343 (17) 0.0122 (18)
Cl1 0.0657 (6) 0.1390 (9) 0.1189 (8) 0.0021 (5) 0.0469 (6) 0.0093 (6)
N1 0.0576 (16) 0.0555 (15) 0.0681 (16) −0.0068 (13) 0.0322 (13) −0.0118 (13)
O3 0.0622 (13) 0.0726 (12) 0.0763 (13) −0.0053 (10) 0.0360 (11) −0.0183 (11)
O2 0.0560 (13) 0.0685 (12) 0.0694 (13) −0.0070 (10) 0.0304 (11) −0.0138 (10)
C14 0.0581 (19) 0.0553 (17) 0.0522 (18) 0.0026 (15) 0.0264 (16) 0.0028 (14)
C8 0.0513 (17) 0.0527 (15) 0.0506 (16) −0.0041 (13) 0.0202 (14) 0.0055 (14)
C7 0.068 (2) 0.0570 (18) 0.0555 (18) 0.0000 (16) 0.0298 (16) 0.0024 (15)
C13 0.0515 (17) 0.0564 (16) 0.0514 (17) −0.0007 (14) 0.0228 (14) 0.0040 (14)
C1 0.0608 (19) 0.0581 (17) 0.0554 (18) 0.0033 (15) 0.0302 (16) 0.0025 (14)
C12 0.0564 (19) 0.074 (2) 0.071 (2) −0.0005 (16) 0.0314 (16) 0.0024 (16)
Geometric parameters (Å, º)
O1—C7 1.219 (3) C6—H6 0.9300
C5—C4 1.371 (4) C3—C4 1.360 (4)
C5—C6 1.379 (4) C3—H3 0.9300
C5—H5 0.9300 C4—Cl1 1.734 (3)
C10—C11 1.378 (4) N1—C7 1.357 (3)
C10—C9 1.380 (4) N1—C8 1.402 (3)
C10—H10 0.9300 N1—NH1 0.93 (3)
C9—C8 1.401 (4) O3—C14 1.315 (3)
C9—H9 0.9300 O3—OH3 0.8200
C2—C3 1.378 (4) O2—C14 1.233 (3)
C2—C1 1.382 (4) C14—C13 1.476 (4)
C2—H2 0.9300 C8—C13 1.406 (4)
C11—C12 1.373 (4) C7—C1 1.501 (4)
C11—H11 0.9300 C13—C12 1.396 (4)
C6—C1 1.377 (4) C12—H12 0.9300
C4—C5—C6 119.1 (3) C5—C4—Cl1 119.4 (3)
C4—C5—H5 120.5 C7—N1—C8 128.6 (3)
C6—C5—H5 120.5 C7—N1—NH1 118 (2)
C11—C10—C9 121.4 (3) C8—N1—NH1 113 (2)
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sup-5 Acta Cryst. (2015). E71, o856–o857
C10—C9—H9 120.0 O3—C14—C13 114.3 (3)
C8—C9—H9 120.0 C9—C8—N1 121.3 (3)
C3—C2—C1 121.0 (3) C9—C8—C13 119.0 (3)
C3—C2—H2 119.5 N1—C8—C13 119.7 (2)
C1—C2—H2 119.5 O1—C7—N1 124.0 (3)
C12—C11—C10 119.1 (3) O1—C7—C1 120.8 (3)
C12—C11—H11 120.5 N1—C7—C1 115.1 (3)
C10—C11—H11 120.5 C12—C13—C8 119.1 (3)
C1—C6—C5 121.5 (3) C12—C13—C14 118.3 (3)
C1—C6—H6 119.2 C8—C13—C14 122.6 (3)
C5—C6—H6 119.2 C6—C1—C2 117.9 (3)
C4—C3—C2 119.8 (3) C6—C1—C7 117.3 (3)
C4—C3—H3 120.1 C2—C1—C7 124.9 (3)
C2—C3—H3 120.1 C11—C12—C13 121.5 (3)
C3—C4—C5 120.7 (3) C11—C12—H12 119.2
C3—C4—Cl1 119.9 (3) C13—C12—H12 119.2
C11—C10—C9—C8 0.4 (4) N1—C8—C13—C14 −1.4 (4)
C9—C10—C11—C12 −0.7 (5) O2—C14—C13—C12 179.1 (3)
C4—C5—C6—C1 0.2 (5) O3—C14—C13—C12 −0.2 (3)
C1—C2—C3—C4 0.4 (5) O2—C14—C13—C8 −0.8 (4)
C2—C3—C4—C5 −0.4 (5) O3—C14—C13—C8 179.9 (2)
C2—C3—C4—Cl1 179.4 (2) C5—C6—C1—C2 −0.2 (4)
C6—C5—C4—C3 0.1 (5) C5—C6—C1—C7 −179.6 (3)
C6—C5—C4—Cl1 −179.7 (2) C3—C2—C1—C6 −0.1 (4)
C10—C9—C8—N1 −178.9 (2) C3—C2—C1—C7 179.3 (3)
C10—C9—C8—C13 0.1 (4) O1—C7—C1—C6 15.5 (4)
C7—N1—C8—C9 −18.7 (4) N1—C7—C1—C6 −166.6 (2)
C7—N1—C8—C13 162.3 (3) O1—C7—C1—C2 −163.9 (3)
C8—N1—C7—O1 3.2 (5) N1—C7—C1—C2 14.0 (4)
C8—N1—C7—C1 −174.6 (2) C10—C11—C12—C13 0.4 (4)
C9—C8—C13—C12 −0.3 (4) C8—C13—C12—C11 0.1 (4)
N1—C8—C13—C12 178.7 (2) C14—C13—C12—C11 −179.8 (2)
C9—C8—C13—C14 179.6 (2)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N1—NH1···O2 0.93 (3) 1.96 (3) 2.678 (3) 133 (3)
O3—OH3···O2i 0.82 1.83 2.645 (3) 175
